Process for the production of polyepoxy silicate resins

ABSTRACT

Alkali metal aldehyde lignin-cellulose silicate polymers are reacted chemically with an epihalohydrin compound to produce a polyepoxy silicate resin; the polyepoxy silicate resin may be cured by a catalyst, e.g., an amine or Lewis acid, to produce a cured epoxy resin, solid or cellular solid product which may be used as an adhesive, as construction sheets, etc.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent applicationSer. No. 257,126, filed on Apr. 24, 1981, now U.S. Pat. No. 4,313,857,which is a continuation-in-part of copending U.S. patent application,Ser. No. 203,730, filed on Nov. 3, 1980, now U.S. Pat. No. 4,281,110,which is a continuation-in-part of U.S. patent application Ser. No.112,290, filed on Jan. 15, 1980, now U.S. Pat. No. 4,243,757, which is acontinuation-in-part of my U.S. patent application, Ser. No. 029,202,filed on Apr. 12, 1979, now U.S. Pat. No. 4,220,757.

SUMMARY OF THE INVENTION

This invention relates to the production of polyepoxy silicate resins bychemically reacting a polyfunctional epoxy compound such as anepihalohydrin with broken-down alkali metal aldehyde lignin-cellulosesilicate polymers. The polyepoxy silicate resin is then cured with acuring agent (catalyst) such as a polyamine or a Lewis catalyst.

The processes for producing the broken-down alkali metal plant silicatepolymer and alkali metal aldehyde lignin-cellulose silicate polymer areoutlined in U.S. patent application Ser. No. 029,202, filed on Apr. 12,1979, now U.S. Pat. No. 4,220,757, by David H. Blount, M.D., and areincorporated into this application.

Polyepoxy compounds and resins and phenoxy resins may be mixed with thealdehyde lignin-cellulose silicate polyepoxy resin and then cured by acatalyst. An excess of polyfunctional epoxide compound may be used withthe aldehyde lignin-cellulose silicate polyepoxy resin as a diluentwhich will also speed up the curing reaction to decrease the curingtime.

Any suitable modifying or additive compounds may be used in the reactionof this invention to vary properties of the product. Typical additivesinclude halohydrins, aldehydes, polyhydroxy compounds, dicarboxylicanhydrides, polysulfide polymers, alkali polysulfides, aminoplasts,phenoplasts, fatty or rosin acid, furfuralketone resins, dibutylphthalate, tricresyl phosphate, polyamides, fatty diamines, styreneoxide, propylene oxide, acetonitriles, primary aromatic sulfonamides,secondary aromatic sulfonamides, polymerized oils, carbon disulfide,soya bean oil, alicyclic anhydrides, aminoplast silicates, phenoplastsilicates, alkali metal polysulfide silicates, acrylic silicates,acrylic monomers, vinyl acetate, acrylonitrile, phenol compounds andother organic compounds and polymers.

While a variety of epoxy compounds and resins have been produced for anumber of diverse applications, none have the unique propertiespossessed by the compounds of this invention. The aldehydelignin-cellulose silicate polyepoxy resins with a curing agent may beused as adhesives, as molding materials, in casting applications, ascoating agents on wood and metals, in dispersions, as fillers, asprepolymers, reacted with polyisocyanates to produce foams forinsulation and in the production of further compounds.

The primary object of the present invention is to produce aldehydelignin-cellulose silicate polyepoxy resins. Another object is to producean aldehyde lignin-cellulose silicate polyepoxy resin which isrelatively inexpensive and may be cured by heat and/or a curing agent toproduce a useful and novel product. A further object is to producealdehyde lignin-cellulose silicate polyepoxy resin that can be mixedwith a polyepoxy compound and cured by a curing agent to produce auseful and novel product. Still another object is to produce aldehydelignin-cellulose silicate polyepoxy resin that may be mixed with aphenoxy resin and then cured by a curing agent to produce a useful andnovel product. A further object is to produce aldehyde lignin-cellulosesilicate resin that may be mixed with a curing agent, then painted onwood or metal and used as a coating agent and/or an adhesive.

The aldehyde lignin-cellulose silicate polyepoxy resins may be modifiedto contain free hydroxyl groups by adding halohydrin, mono-epoxidecompounds, e.g., alkyleneoxide, tetrahydrofuran, styrene oxide,polyhydroxy compounds, and mixtures thereof to the Components A and B toproduce a liquid lignin-cellulose silicate polyepoxy resin which may bereacted with polyisocyanates to produce polyurethane rigid foams andsolid products. The foams may be used for thermal and sound insulation,in construction panels, in art objects, etc. Amines such as tertiaryamines which contain hydrogen atoms which are reactive with isocyanategroups, e.g., triethanolamine, triisosopanolamine may be added with themodifying compounds, halohydrins, mono-epoxide compounds, polyhydroxycompound and mixtures thereof to produce a liquid aldehydelignin-cellulose silicate polyepoxy resin which contains free hydroxylgroups and contains a polyisocyanate catalyst. This resin will reactwith polyisocyanates to produce polyurethane resinous products and foam.

Aldehyde lignin-cellulose silicate polyepoxy resins are produced bymixing and reacting the following components:

A. Polyfunctional epoxide compound;

B. Broken-down alkali metal aldehyde lignin-cellulose silicate polymer.

Aldehyde lignin-cellulose silicate polyepoxy resins are cured by thefollowing catalysts:

(a) amines;

(b) Lewis acids;

(c) alkali metal oxides or hydroxides;

(d) mercaptans;

(e) compounds containing hydrogen replaced by sodium;

(f) phenols, phenol silicates;

(g) alcohols, organic hydroxy silicates;

(h) alicyclic anhydrides, organic polyanhydrides;

(i) aminosilicates with free amine groups;

(j) phenoplasts and aminoplasts;

(k) phenoplast silicates and aminoplast silicates;

(l) polyamides, polyamide silicates;

(m) heat to between 80° C. and 200° C.

Component A

Any suitable polyfunctional epoxide compounds may be used in thisinvention. Suitable polyfunctional epoxide compounds include substitutedepoxide compounds such as epihalohydrin, di-epiiodohydrin,epifluorohydrin, epiiodohydrin and substituted butylene oxides, e.g.,trichlorobutylene oxide and mixtures thereof. Epichlorohydrin is thepreferred polyfunctional epoxide compound.

Component B

The broken-down water-soluble alkali metal plant silicate polymer isproduced by heating a mixture of 3 parts by weight of acellulose-containing plant with 2 to 5 parts by weight of an alkalimetal hydroxide and 1 to 2 parts by weight of an oxidated siliconcompound at 150° C. to 220° C. while agitating for 5 to 60 minutes. Thebroken-down alkali metal cellulose silicate polymer is soluble in water,alcohols, polyols and other organic solvents and is a thick liquid above150° C. and a brown solid below 150° C. The broken-down alkali metalplant silicate polymer has lost a carbon dioxide radical from eachmolecule and the lignin-cellulose bond appears to be intact. When aplant product (cellulose) with the lignin removed is used in theproduction of broken-down alkali metal plant silicate polymer, adark-brown-colored water-soluble polymer is produced.

The alkali metal aldehyde lignin-cellulose silicate polymer is producedby reacting a suitable aldehyde with the broken-down water-solublealkali metal plant silicate polymer. About 2 parts by weight of thebroken-down water-soluble alkali metal plant silicate polymer are mixedwith 1 to 5 parts by weight of an aldehyde selected from the groupconsisting of formaldehyde, acetaldehyde, propionic aldehyde, furfural,crotonaldehyde, acrolein, benzaldehyde, butyl aldehyde, pentanals,octanals and mixtures thereof, then agitated at a temperature betweenambient temperature and 100° C. for 10 to 120 minutes, thereby producingan alkali metal aldehyde lignin-cellulose silicate polymer. An aqueoussolution of formaldehyde is the preferred aldehyde.

Any suitable alkali metal hydroxide may be used to produce broken-downalkali metal plant silicate polymers; sodium hydroxide is preferred. Anysuitable cellulose-containing plant or plant product may be used toproduce broken-down alkali metal plant silicate polymers such as trees,shrubs, agricultural plants, seaweed, pulp wood, cotton, decomposedcellulose-containing plants such as humus, peat and certain soft browncoal, etc.

SUMMARY OF THE INVENTION

I have discovered that a polyfunctional epoxide compound, preferably apolyfunctional halogenated epoxy compound, e.g., epichlorohydrin, willreact chemically with an alkali metal aldehyde lignin-cellulose silicatepolymer to produce an aldehyde lignin-cellulose silicate polyepoxy resinwhich may be cured by a catalytic amount of a curing agent, e.g.,amines, Lewis acids and alkali compounds.

The chemical reactions of this invention may take place under anysuitable conditions. While many of the reactions will take placeacceptably at ambient temperature and pressure. In some cases, betterresults are obtained at somewhat elevated temperature and pressure.Preferably, the reaction takes place at a temperature between 10° C. andthe boiling temperature of the reactants and at a pressure wherein thegaseous reactants are in either a liquid state or a compressed stste.The reaction is exothermic and, in some cases, it is necessary to coolthe materials.

The components may be mixed in any suitable manner. The preferred methodis to mix the Components A (epoxy compound), and B (an alkali metalaldehyde lignin-cellulose silicate polymer and water) in a closed systemwith an agitator, agitating the mixture at a pressure between ambientand 50 psig and between ambient temperature and the boiling temperatureof the polyfunctional epoxy compound or water for from 30 minutes to 4hours, thereby producing an aldehyde lignin-cellulose silicate polyepoxyresin.

In an alternate method, Component A is added to Component B whileagitating at a temperature between 10° C. and just below the boilingtemperature of the reactants for from 30 minutes to 4 hours.

The water-free aldehyde lignin-cellulose resin may be diluted with asolvent, e.g., epichlorohydrin and ethylene chlorohydrin, then theunreacted aldehyde lignin-cellulose silicate polymer and salt producedin the reaction will be precipitated and may be removed by decantation.The excess polyfunctional epoxy compound may be removed by evaporation.

In an alternate method, an additional step is taken wherein a suitableorganic polyhydroxyl compound is added with the components in the amountof up to 50 parts by weight to 100 parts by weight of Components A andis reacted in the same method used in the preferred method. In certaincases, better results are obtained by utilizing an autoclave withsomewhat elevated pressure.

In another alternate method, an additional step is taken wherein asuitable organic polyepoxy compound and/or resin is mixed with thealdehyde lignin-cellulose silicate polyepoxy resin in the amount of upto 100 parts by weight of the polyepoxy resin to 50 parts by weight ofthe aldehyde lignin-cellulose silicate polyepoxy resin. The mixture isthen cured by a catalytic amount of an epoxy curing agent to produce atough solid product. In certain cases, the mixture may be cured by heat.

In another method, an additional step is taken wherein a phenoxy resinis mixed with the aldehyde lignin-cellulose silicate polyepoxy resin inthe amount of up to 100 parts by weight of the phenoxy resin to 100parts by weight of the aldehyde lignin-cellulose silicate polyepoxyresin. The mixture is then cured by a catalytic amount of an epoxycuring agent, e.g., Lewis acid and/or with heat.

The components may be mixed in any suitable proportions within thefollowing limits:

Component A: 10 to 200 parts by weight;

Component B: 50 parts by weight;

Water: Up to 200 parts by weight to 50 parts by weight of Component B.

An excess of Component A may be used and remain as a solvent or beevaporated out by heating. An excess of the alkali metal aldehydelignin-cellulose silicate polymer should be avoided because it will actas a curing agent and cure the aldehyde lignin-cellulose silicatepolyepoxy resin into a solid product.

The additives may be added in any suitable proportions, within thefollowing range:

(a) Curing agent: Up to 200 parts by weight of a curing agent to 100parts by weight of the aldehyde lignin-cellulose silicate polyepoxyresin;

(b) Polyhydroxyl compound: Up to 50 parts by weight to each 50 parts byweight of Component B;

(c) Polyepoxy compound and/or resin: Up to 100 parts by weight ofaldehyde lignin-cellulose silicate polyepoxy resin;

(d) Phenoxy resin: Up to 100 parts by weight to each 100 parts by weightof the aldehyde lignin-cellulose silicate polyepoxy resin;

(e) Phenol compound: Up to 50 parts by weight to each 50 parts by weightof Component B;

(f) Halohydrin: Up to 50 parts by weight to each 50 parts by weight ofComponent B;

(g) Mono-epoxide: Up to 100 parts by weight to each 50 parts by weightof Component B.

Curing Catalyst

Any suitable epoxy resin curing catalyst may be used in this invention.Suitable curing catalysts include amines, Lewis acids, alkali metaloxides and hydroxides, and mercaptan-terminated liquid compounds.

The mercaptan-terminated, saturated type of elastomer may cure thealdehyde lignin-cellulose silicate polyepoxy resin at ambient orelevated temperature and may also be mixed with the amine and used as acuring agent. Any mixtures of the various curing agents such as amines,certain Lewis acids, mercaptan-terminated compound and alkali metalcompounds may be used as the curing agent.

Any suitable Lewis acid may be used in this invention. A Lewis acid isany electron acceptor relative to other reagents present in the system.A Lewis acid will tend to accept a pair of electrons furnished by anelectron donor (or Lewis base) in the process of forming a chemicalcompound. A "Lewis acid" is defined for the purpose of this invention asany electron-accepting material relative to the polymer to which it iscomplexed.

Typical Lewis acids are:

quinones, such as:

p-benzo-quinone,

2,5-dichlorobenzoquinone,

2,6-dichlorobenzoquinone,

chloranil,

naphthoquinone-(1,4),

anthraquinone,

2-methylanthraquinone,

1,4-dimethylanthraquinone,

1-chloroanthraquinone,

anthraquinone-2-carboxylic acid,

1,5-dichloroanthraquinone,

1-chloro-4-nitroanthraquinone,

phenanthrene-quinone,

acenaphenequinone,

pyranthrenequinone,

chrysenequinone,

thio-naphthene-quinone,

anthraquinone-1,8-disulfonic acid and anthraquinone-2-aldehyde;

triphthaloylbenzene-aldehydes such as:

bromal,

4-nitrobenzaldehyde,

2,6-dichlorobenzaldehyde-2,

ethoxy-1-naphthalidehyde,

anthracene-9-aldehyde,

pyrene-3-aldehyde,

oxindole-3-aldehyde,

pyridine-2,6-dialdehyde,

biphenyl-4-aldehyde;

organic phosphonic acids such as:

4-chloro-2-nitrobenzene-phosphonic acid nitrophenols, such as4-nitrophenol, picric acid;

acid anhydrides, for example:

acetic-anhydride,

succinic anhydride,

maleic anhydride,

phthalic anhydride,

tetrachlorophthalic anhydride,

perylene-3,4,9,10-tetracarboxylic acid and

chrysene-2,3,8,9-tetracarboxylic anhydride;

di-bromo maleic acid anhydride;

metal halides of the metals and metalloids of the groups 1B, II throughto group VIII of the periodical system, for example:

aluminum chloride,

zinc chloride,

ferric chloride,

tin tetrachloride,

(stannic chloride),

arsenic trichloride,

stannous chloride,

antimony pentachloride,

magnesium chloride,

magnesium bromide,

calcium bromide,

calcium iodide,

strontium bromide,

chromic bromide,

manganous chloride,

cobaltous chloride,

cobaltic chloride,

cupric bromide,

ceric chloride,

chorium chloride,

arsenic tri-iodide;

boron hallide compounds, for example:

boron trifluoride,

boron trichloride;

ketones, such as:

acetophenone,

benzophenone,

2-acetylnaphthalene,

benzil,

benzoin,

5-benzoylacenaphthene,

biacene-dione,

9-acetyl-anthracene,

9-benzoyl-anthracene,

4-(4-dimethyl-amino-cinnamoyl)-1-acetylbenzene,

acetoacetic acid anilide,

indandione-(1,3),

(1,3-diketohydrindene),

acenaphthene quinone-dichloride,

anisil,

2,2-puridil and

furil.

Additional Lewis acids are mineral acids such as:

the hydrogen halides,

sulphuric acid and

phosphoric acid;

organic carboxylic acids, such as:

acetic acid and the substitution products thereof,

monochloro-acetic acid,

dichloroacetic acid,

trichloroacetic acid,

phenylacetic acid,

7-methylcoumarinylacetic acid (4);

maleic acid,

cinnamic acid,

benzoic acid,

1-(4-diethyl-amino-benzoyl)-benzene-2-carboxylic acid,

phthalic acid,

and tetra-chlorophthalic acid,

alpha-beta-dibromo-beta-formyl-acrylic acid (mucobromic acid),

dibromo-maleic acid,

2-bromo-benzoic acid,

gallic acid,

3-nitro-2-hydroxy-1-benzoic acid,

2-nitro phenoxy-acetic acid,

2-nitro-benzoic acid,

3-nitro-benzoic acid,

4-nitro-benzoic acid,

2-chloro-4-nitro-1-benzoic acid,

3-nitro-4-methoxy-benzoic acid,

4-nitro-1-methyl-benzoic acid,

2-chloro-5-nitro-1-benzoic acid,

3-chloro-6-nitro-1-benzoic acid,

4-chloro-3-nitro-1-benzoic acid,

5-chloro-3-nitro-2-hydroxybenzoic acid,

4-chloro-1-hydroxy-benzoic acid,

2,4-dinitro-1-benzoic acid,

2-bromo-5-nitro-benzoic acid,

4-chlorophenyl-acetic acid,

2-chloro-cinnamic acid,

2-cyana-cinnamic acid,

2,4-dichlorobenzoic acid,

3,5-dinitro-benzoic acid,

3,5-dinitro-salycylic acid,

malonic acid,

mucic acid,

acetosalycylic acid,

benzilic acid,

butane-tetra-carboxylic acid,

citric acid,

cyano-acetic acid,

cyclo-hexane-dicarboxylic acid,

cyclo-hexane-carboxylic acid,

1,10-dichlorostearic acid,

fumaric acid,

itaconic acid,

levulinic acid,

(levulic acid),

malic acid,

succinic acid,

alpha-bromo stearic acid,

citraconic acid,

dibromo-succinic acid,

pyrene-2,3,7,8-tetra-carboxylic acid,

tartaric acid;

organic sulphonic acids, such as:

4-toluene sulphonic acid, and

benzene sulphonic acid,

2,4-dinitro-1-methyl-benzene-6-sulphonic acid,

2,6-dinitro-1-hydroxy-benzene-4-sulphonic acid,

2-nitro-1-hydroxy-benzene-4-sulphonic acid,

4-nitro-1-hydroxy-2-benzene-sulphonic acid,

3-nitro-2-methyl-1-hydroxy-benzene-5-sulphonic acid,

6-nitro-4-methyl-1-hydroxy-benzene-2-sulphonic acid,

4-chloro-1-hydroxy-benzene-3-sulphonic acid,

2-chloro-3-nitro-1-methyl-benzene-5-sulphonic acid and

2-chloro-1-methyl-benzene-4-sulphonic acid.

Any suitable organic amine may be used as the curing agent; however,polyamines are preferred.

The polyamines to be used in this invention include those organicmaterials possessing a plurality of amino hydrogen, e.g., a pluralityof: ##STR1## groups wherein N is an amino nitrogen. These include thealiphatic, cycloaliphatic, aromatic or heterocyclic polyamines as wellas derivatives thereof as long as the derivatives still contain thenecessary amino hydrogen.

Suitable examples of these materials include, among others, thealiphatic polyamines such as, for example, ethylenediamine;diethylenetricamine; triethylenetetramine; tetraethylenepentamine;1,4-diaminobutane; 1,3-diaminobutane; hexamethylenediamine;3-(N-isopropylamine) propylamine; N,N'-diethyl-1,3-propanediamine;hexapropylene-heptamine; penta(1-methyl-propylene hexamine);tri(1,2,2-trimethylethylene) tetramine; tetra(1,3-dimethylpropylene)pentamine; penta-(1,5-dimethylamylene) hexamine;penta(1,2-dimethyl-1-isopropylethylene) hexamine andN,N'-dibutyl-1,6-hexanediamine.

Suitable aliphatic polyamines are the alkylene polyamines of theformula:

    H.sub.2 N(RNH).sub.n H

wherein R is an alkylene radical or a hydrogen-substituted alkyleneradical, and n is an integer of at least one, there being no upper limitto the number of alkylene groups in the molecule.

The aliphatic polyamines are preferred which comprise the polyethylenepolyamines of the formula: ##STR2## wherein n is an integer varying fromabout 2 to 8. A mixture of high-molecular-weight polyethylene polyaminesand diethylenetriamine is especially preferred.

Suitable polyamines include polymeric polyamines, such as may beobtained by polymerizing or copolymerizing unsaturated amines, such asallyl amine or diallyl amine, alone or with other ethylenicallyunsaturated compounds. Alternatively, such polymeric products may alsobe obtained from polymers or copolymers having groups reactive withamines such as, for example, aldehyde groups, as present on acrolein andmethacrolein polymers, and reacting these materials with monomericamines to form the new polymeric polyamines. Polymeric amines can alsobe formed by preparing polymers containing ester groups, such as, forexample, a copolymer of octadecene-1 and methylacrylate, and thenreacting this with a polyamine so as to effect an exchange of an estergroup for an amide group and leave the other amine group or groups free.Polymers of this type are described in U.S. Pat. No. 2,912,416.

Suitable polyamines include the polyamines possessing cycloaliphaticring or rings, such as, for example:

1-cyclohexylamine-3-aminopropane;

1,4-diaminocyclohexane;

1,3-diaminocyclopentane;

di(aminocyclohexyl) methane;

di(aminocyclohexyl) sulfone;

1,3-di(aminocyclohexyl) propane;

2,4-diaminocyclohexane;

N,N'-diethyl-1,4-diaminocyclohexane, and the like.

Preferred members of this group comprise those polyamines having atleast one amino or alkyl-substituted amino group attached directly to acycloaliphatic ring containing 5 to 7 carbon atoms.

Other suitable polyamines comprise the aminoalkylsubstituted aromaticcompounds such as, for example, di(amino-ethyl) benzene, di(aminomethyl)benzene, tri(aminoethyl) benzene, tri(aminobutyl) naphthalene and thelike.

Suitable polyamines also include the organo-metallic compounds, such asthose having a silicon or boron atom or atoms linked to amino orsubstituted amino groups. The compounds may also be thoseorgano-metallic compounds wherein the amino group or substituted aminogroups are attached to carbon, such as in the allosilylpropylamines liketriethoxy silylpropylamines.

Other suitable polyamines include the N-(aminoalkyl) piperazines, suchas, for example, N-aminobutylpiperazine;N-aminoisopropyl-3-butoxypiperazine; N-aminoethylpiperazine;2,5-dioctyl-N-aminoisobutylpiperazine and the like.

Another group of suitable materials is obtained by reacting theabove-described polyamines with a monoepoxide. Examples of thesereactants include, among others, ethylene oxide, propylene oxide,styrene oxide, phenyl glycidyl ether, allyl glycidyl ether, octadecylglycidyl ether, tolyl glycidal ether, chlorophenyl glycidyl ether,naphthyl glycidyl ether, diacetate of monoglycidyl ether of glycerol,dipropionate of the monoglycidyl ether of glycerol, epichlorohydrin,1,2-dicylene oxide, glycidyl acetate, glycidyl benzoate, glycidylpropionate, glycidyl acrylate, glycidyl methyl maleate, glycidylstearate, glycidyl oleate, butyl 1,2-epoxypropionate and the like. Thisreaction between polyamines and monoepoxide is effected merely bybringing the components together in proper proportion. The adducts areobtained when a mol of the polyamine is reacted with not more than onemol of monoepoxide. The excess amine can be retained or can be removedby distillation. Examples of the monoepoxide polyamine reaction productsinclude, among others, N(hydroxy-propyl) diethylenetriamine (reactionproduct of propylene oxide and diethylenetriamine) andN(2-hydroxy-3-phenoxypropyl) diethylenetriamine (reaction product ofphenyl glycidyl ether and diethylenetriamine).

A group of related materials are those soluble fusible products obtainedby reacting a polyepoxide with a monoamine. Examples of polyepoxidesthat may be used include any of the present invention. Examples ofmonoamines include any of those noted above for use in the compositionsof the present invention. Examples of the monoamines include, amongothers, secondary amines such as dimethylamine, diethylamine,dipropylamine, dibutylamine, di(tert-butyl) amine, dinonylamine,dicyclohexylamine, diallylamine, dibenzylamine, methylethylamine,ethylcyclohexylamine, and the like. This reaction between thepolyepoxides and monoamines is effected by merely bringing thecomponents together in proper proportions. The desired soluble fusibleproducts are obtained when the polyepoxide and monoamine are combined soas to have at least 1.5 mols of the amine per epoxide equivalent of thepolyepoxide.

Other examples include the soluble reaction products of polyepoxides andpolyamines and salts thereof, such as described in U.S. Pat. Nos.2,640,037 and 2,643,239.

Still other derivatives that may be employed include those obtained byreacting the polyamines with acrylates, such as methyl acrylate, ethylacrylate, methyl methacrylates and the like. In this case, there is anexchange of the ester linkage for an amide linkage, one of the polyaminenitrogen being involved in the said amine linkage.

Another suitable group of derivatives that may be used in the process ofthe invention include those soluble and fusible products obtained byreacting the polyamines noted above with unsaturated nitriles, such asacrylonitrile. Examples of such products include the cyanoethylateddiethylenetriamine, cyanoethylated tri-ethylenetetramine, cyanoethylatedhexamethylenediamine, cyanoethylated 1,3-propanediamine andcyanoethylated 1,3-diaminocyclohexane. Preferred species of thecyanoalkylated polyamines include those of the formula: ##STR3## whereinx represents an integer in the range of 0 through 3 and A and A'represent a member selected from the group consisting of hydrogen andcyanoethyl radicals, and further characterized in that the amine has atleast one cyanoethyl group and at least one non-tertiary amino group inthe molecule. The preferred members of this group comprise thecyanoethylated aliphatic and cycloaliphatic polyamines containing up to18 carbon atoms.

Other suitable materials include the imidazoline compounds as preparedby reacting monocarboxylic acids with polyamines. These may berepresented by the formula: ##STR4## wherein X is an organic radical andpreferably an alkylene radical, R is a long-chain hydrocarbon radical,and preferably one containing at least 12 carbon atoms, and R' is anorganic radical containing an amine or amine-substituted group.Particularly preferred members of this group are those obtained byreacting any of the above-described polyamines with long-chainmonocarboxylic acids, such as those containing at least 12 and,preferably, 16 to 30 carbon atoms, such as, for example, palmitic acid,pentadecanoic acid, 4-ketomyristic acid, 8,10-dibromostearic acid,margaric acid, stearic acid, alphachlorostearic acid, linoleic acid,oleic acid, dehydroxystearic acid, arachidic acid, cluopanodonic acid,behenic acid, lignoceric acid, cerotic acid, montanic acid, melissicacid, and the like, and mixtures thereof. These imidazolines areprepared by heating the polyamine with the monocarboxylic acid andremoving the water formed by the reaction. The acid and polyamine arecombined in an equivalent ratio varying from about 0.3 to 0.7 to 1, andpreferably about 0.3 to 0.5 to 1. The temperature employed preferablyvaries from about 100° C. to 250° C.

Suitable polyamines include the aromatic polyamines, especially thosehaving at least two --NH₂ groups attached to aromatic ring or rings andcontaining up to 25 carbon atoms.

Suitable polyamines include the sulfur- and/or phosphorous-containingpolyamines such as may be obtained by reacting a mercaptan- orphosphine-containing active hydrogen with an epoxy halide to form ahalohydrin, dihydrochlorinating and then reacting the resulting compoundwith a polyamine, N-(3-ethylthio-2-hydropropyl) diethylenetriamine maybe prepared, for example, by reacting ethyl mercaptan withepichlorohydrin, dihydrochlorinating and then reacting the resultingepoxy compound with diethylenetriamine. Suitable examples of suchcompounds include, among others:

N-(3-butylthio-2-hydroxypropyl) triethylenetetramine,

N-(4-phenylthio-3-hydrobutyl) pentamethylenetetramine,

N-(4-cyclohexylthio-3-hydrobutyl) ethylenediamine,

N-3-cyclohexylthio-2-hydropropyl) hexamethylenediamine,

N-(3-diphenylphosphino-2-hydroxypropyl) triethylenetetramine,

N-(3-dicyclohexylphosphino-2-hydroxypropyl) pentamethylenetetramine,

N-(3-dididecylphosphino-2-hydroxyhexyl) diethylenetriamine, and

N-(3-allylthio-2-hydroxypropyl) hexamethylenediamine.

The N-(allylthio-hydroxyallyl) aliphatic and aromatic polyamines, theN-(cycloalkylthiohydroxy-alkyl) aliphatic and aromatic polyamines andthe N-(arylthiohydroxyalkyl) aliphatic and aromatic polyamines may alsobe used in this invention. Preferred phosphorus-containing curing agentsinclude the N-(dialkylphosphinohydroxyalkyl) aliphatic and aromaticpolyamines, the N-(dicycloalkyl phosphinohydroxyalkyl) aliphatic andaromatic polyamines and the N-(diaryl-phosphinohydroxyalkyl) aliphaticand aromatic polyamines.

Suitable polyamines include the polyamines of the formula: ##STR5##wherein x is an integer of 0 to 10 and R is bivalent aliphatic orcycloaliphatic hydrocarbon radical containing from 1 to 10 carbon atoms,and derivatives obtained by reacting the aforedescribed polyamines withmonoepoxides containing from 2 to 10 carbon atoms, ethylenicallyunsaturated mononitriles containing 1 to 6 carbon atoms.

Salts of polyamines and fatty acid (e.g., stearic, linoleic acid,decanoic acid, lauric acid, oleic acids and the like) may be used inthis invention.

Aminoplasts, phenoplasts, aminoplast silicates, phenoplast silicates,aminosilicate compounds and mixtures thereof, or with other curingagents, may be used as curing agents. These types of curing agentusually require curing at high temperatures and, in some cases, a smallamount of an acid catalyst.

Suitable organic polyhydroxyl compound may be added with thepolyfunctional epoxy compound (Component A) to produce an aldehydelignin-cellulose polyepoxy resin. Suitable polyhydroxyl compoundsinclude di(mono-hydroxy) alkanes, poly(mono-hydroxyl) alkanes anddi(monohydroxyaryl)-alkanes. Other hydroxy-containing compounds such asresorcinol, hydroquinone glycols, glycerol and mixtures thereof. Bestresults are obtained when using [bisphenol-A,2,2-(4-bishydroxyl-phenyl)-propane], in the preparation of the aldehydelignin-cellulose polyepoxy resin.

Typical di(monohydroxyaryl)-alkanes are:

2,2'-bis(3.5-dibromo-4-hydroxy-phenyl)-propane,

2,2'-bis(3,5-dichloro-4-hydroxy-phenyl)-propane,

(4,4'-dihydroxy-diphenyl)-methane,

2,2-(4-bis-hydroxy-phenyl)-propane,

1,1-(4,4'-dihydroxy-diphenyl)-cyclohexane,

1,1-(4,4'-dihydroxy-3,3'-dimethyl-diphenyl)-cyclohexane,

1,1-(2,2'-dihydroxy-4,4'-dimethyl-diphenyl)-butane,

2,2-(2,2'-dihydroxy-4,4'-di-tert-butyl-butyl-diphenyl)-propane;

1,1'-(4,4'-dihydroxy-diphenyl)-1-phenyl-ethane,

2,2-(4,4'-dihydroxy-diphenyl)-butane,

2,2-(4,4'-dihydroxy-diphenyl)-pentane,

3,3-(4,4'-dihydroxydiphenyl)-pentane,

2,2-(4,4'-dihydroxy-diphenyl)-hexane,

3,3-(4,4'-dihydroxy-diphenyl)-hexane,

2,2-(4,4'-dihydroxy-diphenyl)-4-methyl-pentane(dihydroxy-diphenyl)-heptane,

4,4-(4,4'-dihydroxy-diphenyl)-heptane,

2,2-(4,4'-dihydroxy-diphenyl)-tridecane,

2,2-(4,4'-dihydroxy-3'-methyl-diphenyl)-propane,

2,2-(4,4'-dihydroxy-3-methyl-3'-isopropyl-diphenyl)-butane,

2,2-(3,5,3',5'-tetra-chloro-4,4'-dihydroxy-diphenyl)-propane,

2,2-(3,5,3',5'-tetrabromo-4,4'-dihydroxy-diphenyl)-propane,

(3,3'-dichloro-4,4'-dihydroxy-diphenyl)-methane and

2,2'-(dihydroxy-5,5'-difluoro-diphenyl)-methane,

(4,4'-dihydroxy-diphenyl)-phenyl-methane,

1,1-(4,4'-dihydroxy-diphenyl)-1-phenyl-ethane, and mixtures thereof.

The poly(monohydroxy) alkanes are preferred to be polyols (organicpolyhydroxyl compound), in particular, compounds and/or polymers whichcontain from 2 to 8 hydroxyl groups, especially those with a molecularweight of from 80 to about 10,000 and, preferably, from 1,000 to about6,000, e.g., polyesters, polyethers, polythioethers, polyacetals,polycarbonates, or polyester amides containing at least 2, generallyfrom 2 to 8, but, preferably, from 2 to 4 hydroxyl groups. Compoundswhich contain amino groups, thiol groups or carboxyl groups may be used.Polyhydroxyl compounds (polyols) which already contain urethane or ureagroups, modified or unmodified natural polyols, e.g., castor oil,carbohydrates and starches, may also be used. Additional products ofalkylene oxides with phenolformaldehyde resins or urea-formaldehyderesins are also suitable for the purpose of the invention. Polybutadienepolymers with free hydroxyl groups, polysulfide polymers,polybutadiene-styrene copolymers and butadiene-acrylonitrile copolymerchains are also suitable for the purpose of the invention.

The hydroxyl-group-containing polyesters (polyols) may be, for example,reaction products of polyhydric alcohols, preferably dihydric alcoholsand polybasic, preferably dibasic carboxylic acids. The correspondingpolycarboxylic acid anhydride or corresponding polycarboxylic acidesters of lower alcohols or their mixture may be used instead of thefree polycarboxylic acids for preparing the polyesters. Thepolycarboxylic acid may be aliphatic, cycloaliphatic, aromatic and/orheterocyclic and may be substituted, e.g., with halogen atoms and may beunsaturated. Examples include succinic acid, adipic acid, suberic acid,azelaic acid, sebacic acid, phthalic acid, anhydride, tetrahydrophthalicacid anhydride, hexahydrophthalic acid anhydride, tetrachlorophthalicacid anhydride, glutaric acid anhydride, maleic acid, maleic acidanhydride, fumaric acid, dimeric and trimeric fatty acids such as oleicacid, optionally mixed with monomeric fatty acids, dimethylterephthalateand bis-glycol terephthalate. Any suitable polyhydric alcohol (polyol)may be used such as, for example, ethylene glycol, propylene-1,2- and-1,3-glycol, butylene-1,4- and -2,3-glycol, hexane-1,6-diol,octane-1,8-diol, neopentyl glycol,cyclohexanedimethol-(1,4-bis-hydroxy-methylcyclohexane),2-methyl-propane-1,3-diol, glycerol, trimethylol propane,hexane-1,2,6-triol, butane-1,2,4-triol, trimethylol ethane,pentaerythritol, quinitol, mannitol, xorbitol, glucose, starches,fructose, cane sugar, dextrines, castor oil, methylglycoside, diethyleneglycol, triethylene glycol, tetraethylene glycol, polyethylene glycols,dipropylene glycol, polypropylene glycols, dibutylene glycol andpolybutylene glycols. The polyesters may also contain a proportion ofcarboxyl end groups. Polyesters of lactones, such as ε-caprolactone, orhydroxycarboxylic acids, such as ω-hydroxycaproic acid, may also beused.

The polyethers with at least 2, generally from 2 to 8 and, preferably, 2or 3 hydroxyl groups, used according to the invention, are known and maybe prepared by the polymerization of epoxides, e.g., ethylene oxide,propyleneoxide, butylene oxide, tetrahydrofuran, styrene oxide orepichlorohydrin, each with itself, e.g., in the presence of BF₃, or byaddition of these epoxides, optionally as mixtures or, successively, tostarting components which contain reactive hydrogen atoms such asalcohols or amines, e.g., water, ethylene glycol, propylene-1,3- or-1,2-glycol, trimethylol propane, 4,4'-dihydroxydiphenylpropane,aniline, ammonia, ethanolamine or ethylenediamine. Sucrose polyetherssuch as those described, e.g., in German Pat. Nos. 1,176,358 and1,064,938, may also be used according to this invention. It isfrequently preferred to use polyethers which contain predominantlyprimary OH groups (up to 90% by weight, based on the total OH groupcontent of the polyether). Polyethers modified with vinyl polymers suchas those which may be obtained by polymerizing styrene or acrylonitritein the presence of polyethers (U.S. Pat. Nos. 3,383,351; 3,304,273;3,525,093 and 3,110,695; and German Pat. No. 1,152,536), andpolybutadienes which contain OH groups are also suitable.

By "polythioethers" are meant, in particular, the condensation productsof thiodiglycol with itself and/or with other glycols, dicarboxylicacids, formaldehyde, aminocarboxylic acids or amino alcohols. Theproducts obtained are polythiomixed ethers, polythioether esters orpolythioether ester amides, depending on the co-components.

The polyacetals used may be, for example, the compounds which may beobtained from glycols, e.g., diethylene glycol, triethylene glycol,(4,4'-dihydroxydiphenyldimethylmethane) hexane-diol and formaldehyde.Polyacetals suitable for the invention may also be prepared by thepolymerization of cyclic acetals.

The polycarbonates with hydroxyl groups used may be of the known kind,e.g., those which may be prepared by reacting diols, e.g.,propane-1,3-diol, butane-1,4-diol and/or hexane-1,6-diol or diethyleneglycol, triethylene glycol or tetraethylene glycol, withdiarylcarbonates, e.g., diphenylcarbonate or phosgene.

The polyester amides and polyamides include, e.g., the predominantlylinear condensates obtained from polyvalent saturated and unsaturatedcarboxylic acids or their anhydrides and polyvalent saturated andunsaturated amino alcohols, diamines, polyamines and mixtures thereof.

Suitable polyepoxy compounds and/or resins may be mixed with thealdehyde lignin-cellulose silicate polyepoxy, then cured with the curingagent to produce lignin-cellulose silicate epoxy products.

The polyepoxides to be used by the new process of the invention comprisethose materials possessing more than one, preferably, at least two,vicinal epoxy groups, i.e.; ##STR6## groups. These compounds may besaturated or unsaturated, aliphatic, cycloaliphatic, aromatic orheterocyclic, and may be substituted, such as chlorine, hydroxyl group,ether radicals and the like. They may be monomeric or polymeric. Themost common or conventional epoxy resins are obtained by reactingepichlorohydrin with a polyhydroxyl compound, such as Bisphenol A, inthe presence of a catalyst.

For clarity, many of the polyepoxides, particularly those of thepolymeric type, are described in terms of epoxy equivalent values. Themeaning of this expression is described in U.S. Pat. No. 2,633,458. Thepolyepoxides used in the present process are those having an epoxyequivalency greater than 1.0. Various examples of polyepoxides that maybe used in the process of this invention are given in U.S. Pat. No.2,633,458 and it is to be understood that much of the disclosure of thatpatent which is relative to examples of polyepoxides is incorporated byreference into this specification.

Other examples include the epoxidized esters of the polyethylenicallyunsaturated monocarboxylic acids, such as epoxidized linseed, soybean,perilla, oiticia, tung, walnut and dehydrated castor oil, methyllinoleate, butyl linoleate, ethyl 9,12-octadecadienoate, butyl9,12,15-octadecatrienoate, butyl eleostearate, mono-glycerides of tungoil fatty acids, monoglycerides of soybean oil, sunflower, rapeseed,hempseed, sardine, cottonseed oil and the like.

Another group of the epoxy-containing materials used in the process ofthe invention include the epoxidized esters of unsaturated monohydricalcohols and polycarboxylic acids, such as, for example:di(2,3-epoxybutyl) adipate; di(2,3-epoxybutyl) oxalate;di(3,3-epoxyhexyl) succinate; di(3,4-epoxybutyl) maleate;di(2,3-epoxyoctyl) pimetate; di(2,3-epoxy-butyl) phthalate;di(2,3-epoxyoctyl) tetrahydrophthalate; di(4,5-epoxydodecyl) maleate;di(2,3-epoxybutyl) terephthalate; di(2,3-epoxypentyl) triodipropionate;di(5,6-epoxytetradecyl) diphenyldicarboxylate; di(3,4-epoxybutyl)sulfodibutyrate; tri(2,3-epoxybutyl) 1,2,2-butanetricarboxylate;di(5,6-epoxypentadecyl) 1,2,4-butanetricarboxylate;di(5,6-epoxypentadecyl) tartrate; di(4,5-epoxytetradecyl) maleate;di(2,3-epoxybutyl) azelate; di(3,4-epoxybutyl) citrate;di(5,6-epoxyoctyl) cyclohexane-1,2-dicarboxylate; anddi(4,5-epoxyoctadecyl) malonate.

Another group of the epoxy-containing materials includes thoseepoxidized esters of the unsaturated alcohol and unsaturated carboxylicacids such as 2,3-epoxybutyl 3,4,3,4-epoxypentanoate; 3,4-epoxyhexyl3,4-epoxyoctanoate; 3,4-epoxycyclohexyl 3,4-epoxycyclohexanoate;3,4-epoxycyclohexyl 3,4-epoxyoctanoate; 2,3-epoxycyclohexylmethylepoxycyclohexane carboxylate.

Still another group of the epoxy-containing materials includedepoxidized derivatives of polyethylenically unsaturated polycarboxylicacids such as, for example:

dimethyl 8,9,12,13-diepoxydiconsanedioate;

dibutyl 7,8,11,12-diepoxyoctadecanedioate;

dioctyl 10,11-diethyl-9,9,12,13-diepoxyconsanedioate;

dihexyl 6,7,10,11-diepoxyhexadecanedioate;

didecyl 9-epoxy-ethyl-10,11-epoxyoctadecanedioate;

dibutyl 3-butyl-3,4,5,6-diepoxycyclohexane-1,2-dicarboxylate;

dicyclohexyl 3,4,5,6-diepoxycyclohexane-1,2-dicarboxylate;

dibenzyl 1,2,4,5-diepoxycyclohexane-1,2-dicarboxylate; and5,6,10,11-diepoxyoctadecyl succinate.

Still another group comprises the epoxidized polyesters obtained byreacting an unsaturated polyhydric alcohol and/or unsaturatedpolycarboxylic acid or anhydride groups, such as, for example, thepolyester obtained by reacting 8,9,12,13-diconsanedienedioic acid withethylene glycol; the polyester obtained by reacting diethylene glycolwith 2-cyclohexene-1,4-dicarboxylic acid and the like, and mixturesthereof.

Still another group comprises the epoxidized polyethylenicallyunsaturated hydrocarbons, such as epoxidized 2,2-bis(2-cyclohexenyl)propane, epoxidized vinyl cyclohexene and epoxidized dimer ofcyclopentadiene.

Another group comprises the epoxidized polymers and copolymers ofdiolefins, such as butadiene. Examples of this include, among others,butadiene-acrylonitrile copolymers, butadiene-styrene copolymers and thelike.

Another group comprises the glycidyl-containing nitrogen compounds, suchas diglycidyl aniline and diene triglycidylamine.

The polyepoxides that are particularly preferred for use in thecomposition of the invention are the glycidyl ethers, particularly, theglycidyl ethers of polyhydric phenols and polyhydric alcohols. Theglycidyl ethers of polyhydric phenols are obtained by reactingepichlorohydrin with the desired polyhydric phenols in the presence ofalkali. Polyether A and Polyether B which are described in theabove-noted U.S. Pat. No. 2,633,458 are good examples of polyepoxides ofthis type.

Any suitable phenoxy resin may be cured with the aldehydelignin-cellulose silicate polyepoxy resin by use of a curing catalyst,e.g., Lewis acid.

Suitable phenoxy resins are those comprising recurring units having theformula: ##STR7## wherein R₁ and R₂ are each selected from the groupconsisting of hydrogen and alkyl radicals, the total number of carbonatoms in R₁ and R₂ being up to 12; and n is an integer having a value ofat least two.

The basic chemical structure of phenoxy resins is similar to that ofepoxy resins. Phenoxy resins, however, can be readily distinguished as aseparate and unique resin class, differing from epoxides in severalimportant characteristics, not having terminal, highly-reactive epoxygroups and being stable materials which have infinite shelf life.Phenoxy resins are thermoplastic. The phenoxy resins may be obtained bycondensing epichlorohydrin with a suitable dihydroxy organic compound.Best results are obtained when using Bisphenol-A,[2,2-(4-bishydroxyphenyl)-propane], in the preparation of the resin, andthis is considered to be the preferred polyhydroxy compound. Otherhydroxy-containing compounds such as resorcinol, hydroquinone, glycols,glycerol and mixtures thereof may be used in mixture with, or in lieuof, the hydroxy alkanes if desired. The di(monohydroxyaryl)-alkanes,however, are preferred; with, as noted above, Bisphenol-A, being themost preferred embodiment. The di-(monohydroxyaryl) alkanes werepreviously listed in the invention.

The organic polyhydroxyl compound will react chemically with thepolyfunctional epoxy compound.

The phenoxy resins may be mixed with the aldehyde lignin-cellulosesilicate resin in any suitable proportions. The phenoxy resins may bemixed in the ratio of up to 100 parts by weight to 100 parts by weightof the aldehyde lignin-cellulose silicate resin.

Surface-active additives may also be used according to the invention.Suitable emulsifiers are, e.g., the sodium salts of ricinoleicsulphonates or of fatty acids, or salts of fatty acids with amines,e.g., oleic acid diethylamine or stearic acid diethylamine or stearicacid diethanolamine. Other surface-active additives are alkali metal orammonium salts of sulphonic acids, e.g., dodecylbenzone sulphonic acidor dinaphthyl methane disulphonic acid, or of fatty acids, e.g.,ricinoleic acid, or of polymeric fatty acids.

The aldehyde lignin-cellulose silicate polyepoxy resin may be utilizedas an adhesive by mixing about 2 parts by weight of aldehydelignin-cellulose silicate resin with about 1 part by weight of a curingcatalyst, diethylenetriamine, applying the mixture on two boards, thenplacing them together. The mixture hardens in a short period of time toproduce a solid bond between the boards.

The aldehyde lignin-cellulose silicate polyepoxy resin mixed with acuring catalyst, an amino-terminated vegetable oil reacted withtriethylenetetramine, in about equal proportions, is applied to layersof fiber glass cloth where it solidifies into a solid, reinforced panelwhich may be used in boat construction, building construction,furniture, etc.

The aldehyde lignin-cellulose silicate polyepoxy resin containing anorganic polyhydroxyl compound is diluted with epichlorohydrin until itis fluid, then mixed with a curing agent, an amino-terminated maleicanhydride-diethylene condensation product, then painted on wood. Ithardens in a short period of time to produce a tough, somewhat elasticcoating agent.

The mixture of about equal parts of aldehyde lignin-cellulose silicatepolyepoxy resin and a polyepoxy compound, glycidyl ether of Bisphenol-A,is mixed with about equal parts of the amino-terminated propyleneoxide-diethylenetriamine condensation product, then poured into molds ofuseful objects such as tubes, sheets, knobs, handles, gears, etc. Themixture solidifies in a short period of time, producing the aforesaiduseful objects.

The aldehyde lignin-cellulose silicate polyepoxy resin may be utilizedas a molding material by mixing with about equal parts of a phenoxyresin, condensation product of epichlorohydrin with Bisphenol-A, andmaleic acid in the amount of 15%, based on the total weight of themixture. The mixture is placed in a mold and heated to from about 150°C. to 200° C. for about 30 minutes, thereby producing a hard, toughproduct. The aldehyde lignin-cellulose silicate polyepoxy resincontaining the phenoxy resin may also be used in the production ofelectrophotographic materials.

Typical uses of aldehyde lignin-cellulose silicate polyepoxy resinsinclude protective coating, adhesives, laminates, potting, castings,compression and transfer molding.

Organic and inorganic fillers may be added to the aldehydelignin-cellulose silicate polyepoxy resins. Fillers such as metallicpowder, e.g., Fe-, Al-, Zn-, Cu-metallic oxide powder, sand, asbestos,powdered mica, bentonite, glass fibers, clay, talc, zeolites, expandedclay, C-fibers, graphite, steel wool, bronze or copper cloth, siliconpowder, basalt wool or powder, carbon black, glass powder, lava andpumice particles, wood chips, sawdust, cork, cotton, straw, jute, sisal,hemp, flax, rayon, popcorn, plastic and rubber waste and the like may beadded to the aldehyde lignin-cellulose silicate polyepoxy resins.

Suitable plasticizers, such as dibutyl phthalate, tricresyl phosphates,polysulfides, polyamides and fatty diamines, react with aldehydelignin-cellulose silicate polyepoxy resins and internally plasticize thecured resin.

Suitable reactive diluents may be used, such as epihalohydrins andacetonitriles which also react with the aldehyde lignin-cellulosesilicate polyepoxy resins.

Any suitable phenol compound may be used in this invention, such asphenol, cresols, cresylic acid, creosote, xylenols, cashew nutshellliquid, anacordol; p-tert-butyl phenol; cardol, 2,6-dimethyl phenol;chlorophenol; nitrophenol, phenolic acid extracted from bark (U.S. Pat.No. 3,371,054), and mixtures thereof. The phenols react with Component Aand the aldehyde radical in Component B. The phenols are also solventsfor Component B.

Any suitable halohydrin compound may be used in this invention, such asalkene chlorohydrins, e.g., ethylene chlorohydrin, alphadichlorohydrin,dibromohydrin, di-iodohydrin, glycerol-monochlorohydrin, and mixturesthereof. They will react with both Components A and B. Alkenechlorohydrins have the general formula, wherein R is an alkene: ##STR8##

Any suitable mono-epoxide compound may be used in this invention, suchas alkylene oxide (C₂ -C₄) e.g., ethylene oxide, propylene oxide,butylene oxide, tetrahydrofuran, styrene oxide or mixtures thereof. Itis preferred to add the ethylene oxide at a pressure wherein theethylene oxide is in a liquid state or a compressed state.

Components A and B and a polyfunctional amino curing agent may be mixedand reacted, preferably in an aqueous solution, to produce athermosetting aldehyde lignin-cellulose silicate epoxy resin which maybe used in the production of paper, especially in "wet-strength" typepaper. The aldehyde lignin-cellulose silicate epoxy resin in an aqueoussolution is applied to the cellulose fiber mat, then heated to from 80°C. to 120° C. while being pressed into a sheet of paper.

The aldehyde lignin-cellulose silicate polyepoxy resin may be cured witha polyisocyanate or an isocyanate-terminated polyurethane prepolymer.About 50 to 200 parts by weight of the aldehyde lignin-cellulosesilicate polyepoxy resin are reacted with about 100 parts by weight of apolyisocyanate, thereby producing polyurethane silicate foams andresinous products.

Any suitable polyisocyanate, polyisothiocyanate andisocyanate-terminated polyurethane may be used in this invention toproduce polyurethane foams and resinous products. Suitable organicpolyisocyanates include aliphatic, cycloaliphatic, araliphatic, aromaticand heterocyclic polyisocyanates and mixtures thereof. It is generallypreferred to use commercially readily-available polyisocyanates, e.g.,tolylene-2,4- and -2,6-diisocyanate and any mixture of these isomerswhich are known commercially as "TDI,"polyphenylpolymethylene-isocyanates obtained by aniline-formaldehydecondensation followed by phosgenation which are known commercially as"crude MDI," and modified polyisocyanates. Suitable polyisocyanateswhich may be used according to the invention are described, e.g., by W.Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136.

Polyisocyanate catalyst, up to 10% by weight, percentage based onreactants, may be used in this invention: Tertiary amines, e.g.,triethyleneamine, triethylenediamine, triethanolamine and the like;organo-metallic compounds, e.g., tin acetate, tin octoate, tin dilaurateand the like and mixtures thereof. Other examples of catalysts which maybe used according to the invention and details of their action aredescribed in Kunststoff-Handbuch, Volume VII, published by Vieweg andHochtlen, Carl-Hanser-Verlag, Munich, 1966, e.g., on pages 96 and 102.

Suitable blowing agents in an amount up to 50% by weight, percentagebased on reactants, may be used in this invention, suitable blowingagents including water and chemically inert blowing agents, boilingwithin the range of -25° C. to 80° C., e.g., halogenated alkanes,acetone, ethyl acetate and the like. Other examples of blowing agentsare described in Kunststoff-Handbuch, Volume VII, published by Viewegand Hochtlen, Carl-Hanser-Verlag, Munich, 1966, e.g., on pages 108 and109, 453 to 455 and 507 to 510. Compressed air may also be used as theblowing agent.

Suitable foam stabilizers in an amount up to 20% by weight, percentagebased on reactants, such as water-soluble polyester siloxanes, aredescribed in U.S. Pat. No. 3,629,308. Suitable emulsifiers, which werepreviously listed in this Specification, may be used in an amount up to20% by weight, based on the reactants.

Suitable fire-retardant substances may be used in this invention; thehalogenated paraffins and inorganic salts of phosphoric acid are thepreferred fire-retardant agents which may be used in an amount up to 20%by weight, percentage based on the reactants. Inorganic and organicfillers may be used in producing polyurethane.

DESCRIPTION OF PREFERRED EMBODIMENTS

My invention will be illustrated in greater detail in the specificExamples which follow, which detail the preferred embodiments of myprocess. It should be understood that the scope of my invention is notlimited to the specific processes set out in the Examples. Parts andpercentages are by weight, unless otherwise indicated.

EXAMPLE 1

About 3 parts by weight of lye flakes (NaOH) 1 part by weight ofhydrated silica powder and 2 parts by weight of fir sawdust are mixed,then heated to between 150° C. and 220° C. while agitating at ambientpressure, with care being taken that the mixture does not burn, for 5 to60 minutes or until the mixture softens and expands into a dark-brown,thick liquid when hot. It cools to a solid, thereby producing abroken-down alkali metal plant silicate polymer which is water-solubleand has lost a CO₂ radical per molecule.

Other plant particles may be used in place of fir sawdust, such as:

(a) oak sawdust,

(b) ash sawdust,

(c) seaweed,

(d) cotton,

(e) corn cobs,

(f) cotton stalks,

(g) bagasse,

(h) paper,

(i) oat straw,

(j) grass clippings,

(k) pine sawdust,

(l) equal parts of paper and fir sawdust.

4 parts by weight of the broken-down alkali metal plant silicate polymerare mixed with 4 parts by weight of an aqueous solution containing 37%formaldehyde, then heated to between 70° C. and 100° C. while agitatingfor 30 to 120 minutes, thereby producing alkali metal formaldehydelignin-cellulose silicate polymer.

EXAMPLE 2

About 2 parts by weight of sodium hydroxide are heated to from 150° C.to 220° C.; then 2 parts by weight of a plant particle, listed below,and 1 part by weight of dry granular silicic acid are mixed, then heatedto between 150° C. and 220° C. while agitating at ambient pressure for 5to 60 minutes or until the mixture softens and expands into a thickbrown liquid which solidifies on cooling, thereby producing abroken-down alkali metal plant silicate polymer. The polymer is groundinto small particles.

(a) fir sawdust,

(b) oak sawdust,

(c) beech sawdust,

(d) redwood sawdust,

(e) gum sawdust,

(f) sycamore sawdust,

(g) cotton stalk particles,

(h) mixture of weed particles,

(i) equal mixture of (a) and newspapers,

(j) equal mixture of (a) and cotton,

(k) pine sawdust,

(l) maple sawdust,

(m) elm sawdust,

(n) corn cob particles,

(o) seaweed particles,

(p) cornstalk particles,

(q) bugasse particles,

(r) mixtures thereof.

About 2 parts by weight of the broken-down alkali metal plant silicatepolymer and 1 part by weight of acetaldehyde are mixed, then heated tobetween 70° C. and 100° C. while agitating for 30 to 120 minutes,thereby producing alkali metal acetaldehyde lignin-cellulose silicatepolymer.

EXAMPLE 3

About 10 parts by weight of potassium hydroxide are melted, then 8 partsby weight of plant particle selected from the list below and 4 parts byweight of a hydrated silica are mixed, then heated to between 150° C.and 220° C. while agitating at ambient pressure for 5 to 60 minutes oruntil the mixture softens and expands into a dark-brown, thick liquid,thereby producing a broken-down alkali metal plant silicate polymer. Thepolymer is ground into small particles.

(a) fir sawdust,

(b) pine sawdust,

(c) seaweed particles,

(d) corn cob particles,

(e) corn stalk particles,

(f) ash sawdust,

(g) rice straw particles,

(h) wheat straw particles,

(i) bagasse particles,

(j) oak sawdust,

(k) gum sawdust,

(l) cedar sawdust.

About 4 parts by weight of the broken-down alkali metal plant silicatepolymer and 6 parts by weight of an aqueous solution containing 25%formaldehyde are mixed, then heated to between 70° C. and 100° C. whileagitating for 30 to 120 minutes, thereby producing alkali metalformaldehyde lignin-cellulose silicate polymer.

Other aldehydes may be used in place of formaldehyde, such asacetaldehyde, propionaldehyde, furfural, acrolein, butyl aldehyde,benzaldehyde, paraformaldehyde and mixtures thereof.

EXAMPLE 4

About equal parts by weight of the alkali metal aldehydelignin-cellulose silicate polymer as produced in Example 1a andepichlorohydrin are thoroughly mixed, then heated to just below theboiling temperature of epichlorohydrin while agitating for 30 to 90minutes, thereby producing aldehyde lignin-cellulose silicate polyepoxyresin and sodium chloride.

EXAMPLE 5

About equal parts by weight of the alkali metal aldehydelignin-cellulose silicate polymer as produced in Example 2a, water andepichlorohydrin are mixed, then heated for 30 to 90 minutes at atemperature just below the boiling temperature of epichlorohydrin whileagitating at ambient pressure. The temperature is then elevated to justabove the boiling point of water while agitating so as to evaporate mostof the water, thereby producing aldehyde lignin-cellulose silicatepolyepoxy resin and sodium chloride.

Other polyfunctional epoxide compounds may be used in place ofepichlorohydrin, such as epibromohydrin, methyl epichlorohydrin,epifluorohydrin, epiiodohydrin and trichlorobutylene oxide and mixturesthereof.

EXAMPLE 6

About 2 parts by weight of epichlorohydrin are mixed with 3 parts byweight of the alkali metal aldehyde lignin-cellulose silicate polymerproduced in Example 2b, then heated to just below the boilingtemperature of epichlorohydrin while agitating at ambient temperaturefor 30 to 90 minutes, thereby producing aldehyde lignin-cellulosesilicate polyepoxy resin and sodium chloride.

EXAMPLE 7

About 2 parts by weight of the alkali metal aldehyde lignin-cellulosesilicate polymer as produced in Example 2k and 1 part by weight of waterare mixed, then epichlorohydrin is added in an amount wherein thechlorine atoms and sodium atoms are about equal. The mixture is thenadded to an autoclave with a mixer and heated to just below the boilingtemperature of epichlorohydrin while agitating for 30 to 90 minutes,thereby producing aldehyde lignin-cellulose silicate polyepoxy resin.The resin is then diluted with an organic solvent, such asepichlorohydrin, ethylene chlorohydrin or other solvents. The salt andunreacted sawdust settle to the bottom and the resin is decanted off.The solvent is then removed by distillation, thereby recovering thealdehyde lignin-cellulose silicate epoxy resin.

Other polyfunctional epoxide compounds may be used in place ofepichlorohydrin, such as trichlorobutylene oxide, epibromohydrin, methylepichlorohydrin, epifluorohydrin, epiiodohydrin and mixtures thereof.

EXAMPLE 8

About 4 parts by weight of the alkali metal aldehyde lignin-cellulosesilicate polymer as produced in Example 1b, 2 parts by weight ofepichlorohydrin and 2 parts by weight of trichlorobutylene oxide aremixed in an autoclave, then heated to just below the boiling temperatureof epichlorohydrin while agitating for 30 to 90 minutes at about 30psig, thereby producing an aldehyde lignin-cellulose silicate polyepoxyresin.

EXAMPLE 9

Example 8 is modified by using methyl epichlorohydrin in place oftrichlorobutylene oxide.

EXAMPLE 10

About 4 parts by weight of the alkali metal aldehyde lignin-cellulosesilicate polymer as produced in Example 2i, 1 part by weight of ethylenechlorohydrin and 2 parts by weight of epichlorohydrin are mixed in anautoclave, then heated to just below the boiling temperature ofepichlorohydrin while agitating for 30 to 90 minutes, thereby producingaldehyde lignin-cellulose silicate polyepoxy resin and sodium chloride.

EXAMPLE 11

About 4 parts by weight of the alkali metal aldehyde lignin-cellulosesilicate polymer as produced in Example 3a, 1 part by weight of water, 1part by weight of resorcinol and 4 parts by weight of epichlorohydrinare added to an autoclave, then heated to just below the boiling pointof epichlorohydrin while agitating for 30 to 90 minutes, therebyproducing aldehyde lignin-cellulose silicate polyepoxy resins andpotassium chloride.

EXAMPLE 12

About 2 parts by weight of alkali metal aldehyde lignin-cellulosesilicate polymer as produced in Example 2k, 1 part by weight of thealkali metal aldehyde lignin-cellulose silicate polymer as produced in2g, 2 parts by weight of Bisphenol-A, 1 part by weight of water and anamount of epichlorohydrin wherein the chloride atoms and sodium atomsare about equal are added to an autoclave, then heated to a temperaturejust below the boiling point of epichlorohydrin at 20 psig whileagitating for 30 to 90 minutes, thereby producing an aldehydelignin-cellulose silicate polyepoxy resin.

EXAMPLE 13

About 3 parts by weight of the alkali metal aldehyde lignin-cellulosesilicate polymer as produced in Example 2j, 1 part by weight of glyceroland 3 parts by weight of epichlorohydrin are mixed, then heated to atemperature just below the boiling temperature of epichlorohydrin whileagitating for 30 to 90 minutes, thereby producing aldehydelignin-cellulose silicate polyepoxy resin and salt.

EXAMPLE 14

About 2 parts by weight of alkali metal aldehyde lignin-cellulosesilicate polymer as produced in Example 1c, 2 parts by weight of thealkali metal aldehyde lignin-cellulose silicate polymer as produced inExample 3b, 2 parts by weight of propylene glycol, and 4 parts by weightof epichlorohydrin are added to an autoclave, then heated to just belowthe boiling temperature of epichlorohydrin at 20 psig while agitatingfor 30 to 90 minutes, thereby producing aldehyde lignin-cellulosesilicate polyepoxy resin.

EXAMPLE 15

About 4 parts by weight of the alkali metal aldehyde lignin-cellulosesilicate polymer as produced in Example 2b, 2 parts by weight ofresorcinol and 2 parts by weight of epichlorohydrin are added to anautoclave, then heated to a temperature just below the boiling point ofepichlorohydrin at 15 psig while agitating for 30 to 90 minutes, therebyproducing an aldehyde lignin-cellulose silicate polyepoxy and sodiumchloride.

EXAMPLE 16

About 4 parts by weight of the alkali metal aldehyde lignin-cellulosesilicate polymer as produced in Example 1(l), 1 part by weight ofethylene chlorohydrin, 2 parts by weight of epichlorohydrin and 0.5 partby weight of epibromohydrin are mixed, then heated to a temperature justbelow the boiling temperature of epichlorohydrin while agitating for 30to 90 minutes, thereby producing an aldehyde lignin-cellulose silicatepolyepoxy resin and sodium chloride.

EXAMPLE 17

About 3 parts by weight of the alkali metal aldehyde lignin-cellulosesilicate polymer as produced in Example 2c, 1 part by weight of a liquidformaldehyde phenol resin produced in the presence of an acidic catalystand containing free aldehyde radicals, and 3 parts by weight ofepichlorohydrin are mixed, then heated to just below the boilingtemperature of epichlorohydrin while agitating for 30 to 90 minutes,thereby producing aldehyde lignin-cellulose silicate polyepoxy resin.

EXAMPLE 18

About 3 parts by weight of the alkali metal aldehyde lignin-cellulosesilicate polymer as produced in Example 2a, 1 part by weight of aformaldehyde urea resin containing free aldehyde radicals, and 3 partsby weight of epichlorohydrin are mixed, then heated to just below theboiling temperature of epichlorohydrin while agitating for 30 to 90minutes, thereby producing an aldehyde lignin-cellulose silicatepolyepoxy resin.

EXAMPLE 19

About 3 parts by weight of the alkali metal aldehyde lignin-cellulosesilicate polymer as produced in Example 2a, 1 part by weight of phenoland 5 parts by weight of epichlorohydrin are mixed, then heated to justbelow the boiling temperaof epichlorohydrin while agitating for 30 to 90minutes, thereby producing an aldehyde lignin-cellulose silicatepolyepoxy resin. The resin is then heated to between 80° C. and 150° C.for 3 to 20 minutes, thereby producing a solid epoxy silicate product.The polyepoxy silicate product is ground into a powder, washed withwater, then filtered to remove the salt. The powder is then dried. Thealdehyde lignin-cellulose silicate polyepoxy product is soluble inorganic solvents such as ethylene chlorohydrin, organic polyhydroxycompounds and phenols and may be used as a coating agent on cloth, woodand metal, as an adhesive and as an impregnant. The dried powder mayalso be used as molding powder, being molded into useful objects by heatand pressure. The aldehyde lignin-cellulose silicate polyepoxy powdermay be added to a polyol and reacted with a polyisocyanate to produce astrong, rigid polyurethane silicate foam which may be used forinsulation and other construction uses.

EXAMPLE 20

About equal parts by weight of epichlorohydrin and alkali metal aldehydelignin-cellulose silicate polymer as produced in Example 3d are mixed,then heated to a temperature between ambient temperature and the boilingtemperature of epichlorohydrin while agitating at ambient pressure for30 to 90 minutes, thereby producing aldehyde lignin-cellulose silicatepolyepoxy resin. About equal parts by weight of the polyepoxy silicateresin and phenoxy resin which is produced by reacting epichlorohydrinwith Bisphenol-A are mixed, then about equal parts by weight, based onthe phenoxy resin of phthalic anhydride, are mixed with the mixture ofphenoxy resin and aldehyde lignin-cellulose silicate polyepoxy, thenheated to just above the melting point of phthalic anhydride whileagitating for 10 to 30 minutes, thereby producing an aldehydelignin-cellulose silicate epoxy product. The aldehyde lignin-cellulosesilicate polyepoxy resin, while still in a fluid state, may be pouredinto molds of useful products such as gears, pulley wheels, knobs, etc.Fillers, coloring reagents or reinforcing agents such as fiber glass maybe added to the aldehyde lignin-cellulose silicate epoxy product whilestill in a fluid state.

EXAMPLE 21

About 10 parts by weight of the aldehyde lignin-cellulose silicatepolyepoxy resin as produced in Example 20 and 10 parts by weight of apolyepoxy compound, a glycidil polyether of 2,2-bis(4-hydroxyphenyl)propane containing at least 2 epoxy radicals per molecule, and 10 partsby weight of diethylenetriamine are mixed, then applied to the surfaceof two boards. The boards are placed one on top of the other with theresin between and the resin hardens in 10 to 90 minutes, therebyproducing a strong bond between the two boards.

EXAMPLE 22

About 100 parts by weight of the aldehyde alkali metal lignin-cellulosesilicate polymer as produced in Example 2b, 20 parts by weight ofethylene chlorohydrin, 20 parts by weight of propylene glycol, 10 partsby weight of triethanolamine, 10 parts by weight of epichlorohydrin aremixed, then agitated at ambient temperature and pressure for 10 to 30minutes, thereby producing a liquid aldehyde lignin-cellulose silicateepoxy product.

About equal parts by weight of the liquid aldehyde lignin-cellulosesilicate polyepoxy product and 4,4'-diphenyl methylene diisocyanate aremixed with 10% by weight of a blowing agent, methylene chloride, basedon the weight of the polyisocyanate. The mixture begins to expand inabout 15 seconds and expands to produce a tough, rigid polyurethanesilicate foam which weighs about 1.5 to 2 lbs./cu.ft.; it has a creamtime of 40 to 80 seconds and a tack-free time of 60 to 220 seconds. Thepolyurethane silicate foam has many well known uses such as sound andthermal insulation, door cores, construction components, art objects,floatation in boats, etc.

Other polyisocyanates may be used in place of 4,4'-diphenylmethylenediisocyanate such as tolylene diisocyanate, polyphenyl polymethyleneisocyanates and mixtures thereof.

EXAMPLE 23

About 100 parts by weight of the alkali metal aldehyde lignin-cellulosesilicate polymer as produced in Example 1k, 20 parts by weight ofethylene chlorohydrin, 50 parts by weight of propylene oxide and 100parts by weight of epichlorohydrin are mixed, then 10 parts by weight ofdimethylethanolamine and 5 parts by weight of triethylenediamine areadded and thoroughly mixed at ambient temperature. The mixture is thenagitated for 10 to 30 minutes, thereby producing a liquid aldehydelignin-cellulose silicate epoxy resin.

About 10 parts by weight of the aldehyde lignin-cellulose silicate epoxyresin, 7 parts by weight of crude MDI(polyphenylpolymethylene-isocyanates obtained by aniline-formaldehydecondensation followed by phosgenation) and 2 parts by weight oftrichlorotrifluoroethane are mixed. The mixture expands to produce arigid, tough, light-brown-colored polyurethane silicate foam.

Other polyisocyanates may be used in place of crude MDI such as tolylenediisocyanate, 4,4'-diphenyl methylene diisocyanate and mixtures thereof.

Other epoxide compounds may be used in place of propylene oxide such asbutylene oxide, tetrahydrofuran, styrene oxide and ethylene oxide. It ispreferred to use elevated pressure wherein the ethylene oxide is in aliquid state.

EXAMPLE 24

About equal parts by weight of the aldehyde lignin-cellulose silicatepolyepoxy resin as produced in Example 7 and diethylenetriamine-linoleicacid condensation with at least 2 amine radicals per molecule are mixedat 25° C., then applied between 2 pieces of wood in a thin layer. Theresin is cured within 12 hours and produces a strong bond between thetwo pieces of wood.

EXAMPLE 25

About 10 parts by weight of the aldehyde lignin-cellulose silicatepolyepoxy resin as produced in Example 7 and 5 parts by weight of amercaptan-terminated liquid compound produced by reactingethylenechloride and sodium polysulfide are mixed, then heated in a moldto between 80° C. and 120° C., thereby producing a tough, solid aldehydelignin-cellulose silicate epoxy product.

EXAMPLE 26

About 3 parts by weight of the aldehyde lignin-cellulose silicatepolyepoxy resin as produced in Example 18 are mixed with 2 parts byweight of propyleneoxide-diethylenetriamine resin with at least twoamine radicals on each molecule, then poured into a mold of an artobject and the mixture hardens in 30 minutes to 12 hours to produce analdehyde lignin-cellulose silicate epoxy product.

EXAMPLE 27

About 3 parts by weight of the uncured liquid aldehyde lignin-cellulosesilicate polyepoxy resin as produced in Example 19 are mixed with 2parts by weight of a polyamide with at least two free amine radicals permolecule, then applied on layers of fiber glass. The resin cures toproduce a strong, rigid panel which may be used to build boats,construction panels, containers, etc.

EXAMPLE 28

About equal parts by weight of the aldehyde lignin-cellulose silicatepolyepoxy resin as produced in Example 5, trichlorobutylene oxide andtriethylenetetramine are mixed, then applied to the top surface of twopieces of wood, then the coated surfaces are placed together and after24 hours, a strong bond is obtained between the pieces of wood.

EXAMPLE 29

About 3 parts by weight of the aldehyde lignin-cellulose silicatepolyepoxy resin as produced in Example 17, 0.5 part by weight ofcresylic acid and 3 parts by weight of the reaction product of phenylglycidyl ether and diethylenetriamine containing at least 2 free amineradicals per molecule are mixed, then placed in a crack in a piece ofpolyester fiber glass panel where it is cured within 12 hours, bonds theedges and fills the cavity in the panel.

EXAMPLE 30

About 3 parts by weight of the aldehyde lignin-cellulose silicatepolyepoxy resin as produced in Example 20, 1 part by weight of methylmethacrylate and 2 parts by weight of diethylenetriamine are mixed, thenpoured into a mold for a tool handle. The mixture cures to produce atough solid aldehyde lignin-cellulose silicate epoxy product.

The emulsion may be reacted with a polyisocyanate to produce a foamedproduct which may be used for sound and thermal insulation.

Although specific conditions and ingredients have been described inconjunction with the foregoing examples of preferred embodiments, thesemay be varied, and other reagents and additives may be used wheresuitable, as described above, with similar results.

Other modifications and applications of this invention will occur tothose skilled in the art upon reading this disclosure. These areintended to be included within the scope of this invention, as definedin the appended claims.

I claim:
 1. The process for the production of aldehyde lignin-cellulosesilicate polyepoxy resin by mixing and reacting the followingcomponents:A.: Polyfunctional epoxide compound, 10 to 200 parts byweight, B.: Alkali metal aldehyde broken down lignin-cellulose silicatepolymer, 50 parts by weight.
 2. The process of claim 1 wherein thepolyfunctional epoxide compound is selected from the group consisting ofepichlorohydrin, epibromohydrin, methyl epichlorohydrin,di-epi-iodohydrin, epifluorohydrin, epi-iodohydrin and trichlorobutyleneoxides.
 3. The process of claim 1 wherein the polyfunctional epoxidecompound is epichlorohydrin.
 4. The process of claim 1 wherein up to 200parts by weight of water are added to the alkali metal aldehyde brokendown lignin-cellulose silicate polymer before adding the polyfunctionalepoxide compound.
 5. The process of claim 1 wherein the aldehyde brokendown lignin-cellulose silicate polyepoxy resin is cured by heating. 6.The process of claim 1 wherein an additional step is taken wherein acuring agent in the amount of up to 200 parts by weight, selected fromthe group consisting of an organic amine, Lewis acids, alkali metaloxides and hydroxides, and mercaptan-terminated liquid compounds, isadded to 100 parts by weight of the aldehyde broken downlignin-cellulose silicate polyepoxy resin.
 7. The process of claim 6wherein the curing agent is diethylenetriamine.
 8. The process of claim1 wherein up to 50 parts by weight of a polyhydroxyl compound are mixedwith Components A and B before reacting.
 9. The process of claim 8wherein the organic polyhydroxy compound is selected from the groupconsisting of di(monohydroxy) alkanes, di(monohydroxyaryl)alkanes,resorcinol, hydroquinone glycols, glycerol, trimethylol propane,polyesters with 2 or more hydroxy groups per molecule, polyethers with 2or more hydroxyl groups per molecule, polyamide with 2 or more hydroxylgroups per molecule, and mixtures thereof.
 10. The process of claim 8wherein the organic polyhydroxy compound is Bisphenol-A.
 11. The processof claim 1 wherein up to 50 parts by weight of a phenol compound,selected from the group consisting of phenol, cresole, cresylic acid,creosote, xylenols, cashew nutshell liquid, anacordol, p-tert-butylphenol, p-tert-anyl phenol, phenolic acids produced from bark andmixtures thereof, are added for each 50 parts by weight of Component B.12. The process of claim 1 wherein an additional step is taken whereinup to 100 parts by weight of a polyepoxy compound are mixed with 50parts by weight of the aldehyde broken down lignin-cellulose silicatepolyepoxy resin, then mixed with a curing agent up to an amount byweight equal to the weight of the mixture, thereby producing an aldehydebroken down lignin-cellulose silicate epoxy product.
 13. The process ofclaim 12 wherein the curing catalyst is selected from the groupconsisting of an amine, a Lewis acid, and a mercaptan-terminated liquidcompound.
 14. The process of claim 1 wherein an additional step is takenwherein 100 parts by weight of the aldehyde broken down lignin-cellulosesilicate polyepoxy resin are mixed with up to 100 parts by weight of aphenoxy resin; then up to 200 parts by weight of a curing agent areadmixed at a temperature wherein the mixture is in a liquid state,thereby producing an epoxy product.
 15. The process of claim 14 whereinthe curing agent is selected from the group consisting of an amine, aLewis acid and a mercaptan-terminated compound.
 16. The process of claim14 wherein the curing agent is a Lewis acid.
 17. The process of claim 12wherein the polyepoxy compound is a glycidyl ether of a polyhydriccompound of the group consisting of polyhydric alcohols and polyhydricphenols.
 18. The process of claim 12 wherein the polyepoxy compound is aglycidyl polyether of 2,2-bis(4-hydroxy phenyl) propane, containing atleast 2 epoxy radicals per molecule.
 19. The product produced by theprocess of claim
 1. 20. The product produced by the process of claim 4.21. The product produced by the process of claim
 6. 22. The productproduced by the process of claim
 8. 23. The product produced by theprocess of claim
 11. 24. The product produced by the process of claim12.
 25. The product produced by the process of claim
 13. 26. The processof claim 1 wherein up to 50 parts by weight of a halohydrin compound,selected from the group consisting of alkene halohydrins, are added withComponents A and B.
 27. The process of claim 26 wherein the halohydrinis ethylene chlorohydrin.
 28. The product produced by the process ofclaim
 26. 29. The process of claim 1 wherein an amine catalyst in theamount of up to 200 parts by weight is added with Components A and B.30. The process of claim 29 wherein the amine catalyst is a tertiaryamine.
 31. The product produced by the process of claim
 29. 32. Theprocess of claim 1 wherein up to 100 parts by weight of a mono-epoxidecompound, selected from the group consisting of ethylene oxide,propylene oxide, butylene oxide, tetrahydrofuran styrene oxide ormixtures thereof, are added with Components A and B at a pressurewherein the mono-epoxide compound is in a liquid state or a compressedstate.
 33. The product produced by the process of claim
 32. 34. Theprocess of claim 1 wherein up to 100 parts by weight of an organiccompound, selected from the group consisting of organic hydroxycompounds, organic polyhydroxy compounds, organic mono-epoxide compound,halohydrin compounds, organic polyepoxy compounds, and mixtures thereof,are added with Components A and B, at a pressure wherein the organiccompound is in a liquid state or a compressed state.
 35. The productproduced by the process of claim 34.